The present invention relates to novel aminophosphonium compounds, to substance mixtures containing them, and to the preparation and use thereof.
Aminophosphonium compounds are used, as is evident from WO 98/32532 and WO 98/22413, as catalysts for preparing fluorine-containing compounds by a halogen/fluorine exchange reaction (halex reaction). Although the tetrakis(diethylamino)phosphonium bromide used in WO 98/32532 and WO 98/22413 gives good results, it has a very high dermal toxicity which stands in the way of industrial use, however.
The object is to provide novel compounds which are suitable as catalyst or component of catalyst systems for phase-transfer reactions, in particular for halogen-fluorine exchange reactions, have a lower dermal toxicity and achieve or even exceed the results obtainable on use of tetrakis(diethylamino)phosphonium bromide.
This object is achieved by compounds of the formula 
in which one, two or three of the radicals R1, R2, R3 and R4 are 
where m and n are an integer from 1 to 10, R5, R6, R7 and R8 are, independently of one another, identical or different and are a straight-chain or branched alkyl radical having 1 to 10 carbon atoms, and the remaining radical(s) R1 to R4 are 
or xe2x80x94NR9R10, where R9 and R10 are identical or different and are a straight-chain or branched alkyl radical having 1 to 10 carbon atoms,
and Xxe2x88x92 is an inorganic or organic anion or an equivalent of a multiply charged inorganic or organic anion.
Compounds of interest are those of the formula (1) in which one or two of the radicals R1, R2, R3 and R4 are 
and the remaining radicals R1 to R4 are 
or xe2x80x94NR9R10.
Importance further attaches to compounds of the formula (1) in which m and n are an integer from 1 to 6, and R5, R6, R7, R8, R9 and R10 are identical or different and are a straight-chain or branched alkyl radical having 1 to 4 carbon atoms.
The aforementioned radicals R1, R2, R3 and R4 are, in particular, 
preferably xe2x80x94N{(CH2xe2x80x94CH2xe2x80x94O)mR5}2 or xe2x80x94N{(CH2xe2x80x94CH2xe2x80x94N(R7))nR8}2, particularly preferably xe2x80x94N{(CH2xe2x80x94CH2xe2x80x94O)mR5}2.
The aforementioned remaining radical(s) R1 to R4 are, in particular, 
In the compounds of the formula (1), Xxe2x88x92 is Fxe2x88x92, Clxe2x88x92, Brxe2x88x92, Ixe2x88x92, ClO4xe2x88x92, BF4xe2x88x92, PF6xe2x88x92, NO3xe2x88x92, HSO4xe2x88x92, xc2xd SO42xe2x88x92, H2PO4xe2x88x92, xc2xd HPO42xe2x88x92, ⅓ PO43xe2x88x92, Rxe2x80x2xe2x80x94COOxe2x88x92, where Rxe2x80x2 is an alkyl radical having 1 to 9 carbon atoms, a phenyl radical, benzyl radical or naphthyl radical, Rxe2x80x3xe2x80x94SO3, where Rxe2x80x3 is an alkyl radical having 1 to 18 carbon atoms, a phenyl radical, tolyl radical or naphthyl radical, HCO3xe2x88x92, xc2xd CO32xe2x88x92 or xc2xd C6H4(COOxe2x88x92)2.
Xxe2x88x92 is, in particular, Fxe2x88x92, Clxe2x88x92, Brxe2x88x92, Ixe2x88x92, BF4xe2x88x92, PF6xe2x88x92 or xc2xd SO42xe2x88x92, preferably Fxe2x88x92, Clxe2x88x92, or Brxe2x88x92, particularly preferably Clxe2x88x92.
The following aminophosphonium compounds (aminophosphonium salts) may be mentioned as examples without claiming completeness.
Bis(2-methoxyethyl)amino-tris(pyrrolidino)phosphonium chloride
Di(bis(2-methoxyethyl)amino)-bis(pyrrolidino)phosphonium chloride
Tri(bis(2-methoxyethyl)amino)-(pyrrolidino)phosphonium chloride
Bis(methyl-diethoxyethylene)amino-tris(pyrrolidino)phosphonium chloride
Di(bis(methyl-diethoxyethylene)amino)-bis(pyrrolidino)phosphonium chloride
Tri(bis(methyl-diethoxyethylene)amino)-(pyrrolidino)phosphonium chloride
Bis(methyl-tetraethoxyethylene)amino-tris(pyrrolidino)phosphonium chloride
Di(bis(methyl-tetraethoxyethylene)amino-bis(pyrrolidino)phosphonium chloride
Tri(bis(methyl-tetraethoxyethylene)amino)-(pyrrolidino)phosphonium chloride
Morpholino-tris(pyrrolidino)phosphonium chloride
Dimorpholino-bis(pyrrolidino)phosphonium chloride
Trimorpholino-(pyrrolidino)phosphonium chloride
Bis(2-methoxyethyl)amino-tris(piperidino)phosphonium chloride
Di(bis(2-methoxyethyl)amino)-bis(piperidino)phosphonium chloride
Tri(bis(2-methoxyethyl)amino)-(piperidino)phosphonium chloride
Bis(methyl-diethoxyethylene)amino-tris(piperidino)phosphonium chloride
Di(bis(methyl-diethoxyethylene)amino)-bis(piperidino)phosphonium chloride
Tri(bis(methyl-diethoxyethylene)amino)-(piperidino)phosphonium chloride
Bis(methyl-tetraethoxyethylene)amino-tris(piperidino)phosphonium chloride
Di(bis(methyl-tetraethoxyethylene)amino)-bis(piperidino)phosphonium chloride
Tri(bis(methyl-tetraethoxyethylene)amino)-(piperidino)phosphonium chloride
Morpholino-tris(piperidino)phosphonium chloride
Dimorpholino-bis(piperidino)phosphonium chloride
Bis(2-methoxyethyl)amino-tris(diethylamino)phosphonium chloride
Di(bis(2-methoxyethyl)amino)-bis(diethylamino)phosphonium chloride
Tri(bis(2-methoxyethyl)amino)-(diethylamino)phosphonium chloride
Bis(methyl-tetraethoxyethylene)amino-tris(diethylamino)phosphonium chloride
Di(bis(methyl-tetraethoxyethylene)amino-bis(diethylamino)phosphonium chloride
Tri(bis(methyl-tetraethoxyethylene)amino)-(diethylamino)phosphonium chloride
Morpholino-tris(diethylamino)phosphonium chloride
Dimorpholino-bis(diethylamino)phosphonium chloride
Trimorpholino-(diethylamino)phosphonium chloride
Bis(2-methoxyethyl)amino-tris(dimethylamino)phosphonium chloride
Di(bis(2-methoxyethyl)amino)-bis(dimethylamino)phosphonium chloride
Tri(bis(2-methoxyethyl)amino)-(dimethylamino)phosphonium chloride
Bis(methyl-bisethoxyethylene)amino-tris(dimethylamino)phosphonium chloride
Di(bis(methyl-bisethoxyethylene)amino)-bis(dimethylamino)phosphonium chloride
Tri(bis(methyl-bisethoxyethylene)amino)-(dimethylamino)phosphonium chloride
Bis(methyl-tetraethoxyethylene)amino-tris(dimethylamino)phosphonium chloride
Di(bis(methyl-tetraethoxyethylene)amino)-bis(dimethylamino)phosphonium chloride
Tri(bis(methyl-tetraethoxyethylene)amino)-(dimethylamino)phosphonium chloride
Tris(dimethylamino)-morpholino-phosphonium chloride
Bis(dimethylamino)-dimorpholino-phosphonium chloride
Dimethylamino-trimorpholino-phosphonium chloride
Bis(2-methoxyethyl)amino-tris(butyl-ethylamino)phosphonium chloride
Di(bis(2-methoxyethyl)amino)-bis(butyl-ethylamino)phosphonium chloride
Tri(bis(2-methoxyethyl)amino)-(butyl-ethylamino)phosphonium chloride
Bis(methyl-tetraethoxyethylene)amino-tris(butyl-ethylamino)phosphonium chloride
Di(bis(methyl-tetraethoxyethylene)amino)-bis(butyl-ethylamino)phosphonium chloride
Tri(bis(methyl-tetraethoxyethylene)amino)-(butyl-ethylamino)phosphonium chloride
Tris(butyl-ethylamino)-morpholino-phosphonium chloride
Bis(butyl-ethylamino)-dimorpholino-phosphonium chloride
(Butyl-ethylamino)-trimorpholino-phosphonium chloride
N-Methylpiperazino-tris(pyrrolidino)phosphonium chloride
Bis(N-methylpiperazino)-bis(pyrrolidino)phosphonium chloride
Tris(N-methylpiperazino)-(pyrrolidino)phosphonium chloride
N-Methylpiperazino-tris(diethylamino)phosphonium chloride
Bis(N-methylpiperazino)-bis(diethylamino)phosphonium chloride
Tris(N-methylpiperazino)-(diethylamino)phosphonium chloride
N-Methylpiperazino-tris(dimethylamino)phosphonium chloride
Bis(N-methylpiperazino)-bis(dimethylamino)phosphonium chloride
Tris(N-methylpiperazino)-(dimethylamino)phosphonium chloride
N-Methylpiperazino-tris(butyl-ethylamino)phosphonium chloride
Bis(N-methylpiperazino)-bis(butyl-ethylamino)phosphonium chloride
Tris(N-methylpiperazino)-(butyl-ethylamino)phosphonium chloride
In place of the listed aminophosphonium chlorides it is also possible to employ, for example, the corresponding bromides, iodides, fluorides, sulfates, hydrogen sulfates, acetates or phthalates.
The present invention also relates to mixtures of substances comprising at least one compound of the formula 
in which R1, R2, R3, R4 and Xxe2x88x92 have the above meaning, and at least one compound selected from the group of quaternary ammonium compounds of the formula 
quaternary ammonium salts or phosphonium salts of the formula 
polyethers of the formula R20xe2x80x94(Oxe2x80x94CxH2x)sxe2x80x94OR21 (4) and crown ethers,
in which in formula (2) R11, R12 and R13 are identical or different and are a linear or branched radical of the formula xe2x80x94(CpH2pO)rR15 in which R15 is hydrogen or a linear or branched alkyl radical having 1 to 16 carbon atoms, p is an integer from 1 to 10 and r is an integer from 1 to 15;
or a linear or branched alkyl radical having 1 to 30 carbon atoms;
or an unsubstituted phenyl or naphthyl radical, or a substituted phenyl or naphthyl radical, where the substituents have the meaning of halogen, C1-C4-alkyl, C1-C4-alkoxy, nitro or cyano;
R14 is a linear or branched radical of the formula xe2x80x94(CpH2pO)rR15 and
Yxe2x88x92 is an inorganic anion;
and in formula (3)
R16, R17, R18 and R19 are identical or different and are a linear or branched alkyl radical having 1 to 22 carbon atoms; or an unsubstituted or substituted aryl radical or a C1-C4-alkylaryl radical, where aryl has the meaning of phenyl or naphthyl, and said substituents are halogen,
C1-C4-alkyl, C1-C4-alkoxy, nitro or cyano; Z has the meaning of N or P, and Yxe2x88x92 is an inorganic anion;
and in formula (4)
R20 and R21 are identical or different and are a linear or branched alkyl radical having 1 to 16 carbon atoms;
x is an integer from 2 to 6 and
s is an integer from 1 to 60;
or one of the radicals R20 and R21 is hydrogen and the other one of the radicals is a linear or branched alkyl radical having 1 to 16 carbon atoms,
x is an integer from 2 to 6 and s is an integer from 2 to 50, or the radicals R20 and R21 are hydrogen, x is an integer from 2 to 6 and s is an integer from 3 to 5.
The present invention relates in particular to mixtures of substances which comprise at least one compound of the formula (1) and at least one compound selected from the group of quaternary ammonium compounds of the formula (2), quaternary ammonium salts and phosphonium salts of the formula (3), polyethers of the formula (4) and crown ethers, in which in formula (2) R11, R12 and R13 are identical or different and are a linear or branched radical of the formula xe2x80x94(CpH2pO)rR15 in which R15 is hydrogen or a linear or branched alkyl radical having 1 to 8 carbon atoms, p is an integer from 1 to 5 and r is an integer from 2 to 10; or a linear or branched alkyl radical having 1 to 18 carbon atoms; or an unsubstituted phenyl or naphthyl radical; R14 is a linear or branched radical of the formula xe2x80x94(CpH2pO)rR15, in which R15 is hydrogen or a linear or branched alkyl radical having 1 to 8 carbon atoms, p is an integer from 1 to 5 and r is an integer from 2 to 10; and Xxe2x88x92 is fluoride, chloride, bromide, SO42xe2x88x92/2 or hydrogen sulfate.
Mixtures of substances of particular interest are those comprising at least one compound of the formula (1) and at least one compound from the group of quaternary ammonium compounds of the formula (2).
Mention should also be made of mixtures of substances of the above type comprising at least one ammonium salt or phosphonium salt of the formula (3), in which in formula (3) R16, R17, R18 and R19 are identical or different and are a linear or branched alkyl radical having 1 to 16 carbon atoms; or an unsubstituted or substituted aryl radical or a C1-C4-alkylaryl radical, where aryl has the meaning of phenyl or naphthyl, and said substituents are halogen, C1-C4-alkyl, C1-C4-alkoxy, nitro or cyano.
Mixtures of substances of the above type comprising at least one polyether of the formula (4) or crown ether, in which in formula (4) R20 and R21 are identical or different and are hydrogen or a linear or branched alkyl radical having 1 to 8 carbon atoms, x is an integer from 2 to 3 and s is an integer from 4 to 50, are likewise of interest.
The mixtures of substances normally comprise from 5 to 95% by weight, in particular 20 to 80% by weight, preferably 25 to 75% by weight, of at least one compound of the formula (1). The residual 95 to 5% by weight, in particular 80 to 20% by weight, preferably 75 to 25% by weight, of the mixtures of substances account for the remainder, namely at least one compound selected from the group of quaternary ammonium compounds of the formula (2) of quaternary ammonium or phosphonium salts of the formula (3), polyethers of the formula (4) and crown ethers, in particular at least one compound from the group of quaternary ammonium compounds of the formula (2).
The present invention further relates to a process for preparing compounds of the formula 
It comprises reacting a phosphorus pentahalide in the presence of an inert solvent at xe2x88x9270 to 140xc2x0 C., in particular xe2x88x9230 to 120xc2x0 C., preferably xe2x88x9215 to 60xc2x0 C., with from 1 to 6 mol, in particular 1 to 2.5 mol, of 
per halogen equivalent to be exchanged, and subsequently reacting the reaction product with from 1 to 10 mol, in particular 1 to 3 mol, of 
or HNR9R10 per halogen equivalent still to be exchanged. This reaction of the reaction product takes place at xe2x88x9215 to 140xc2x0 C., in particular 0 to 130xc2x0 C., preferably 20 to 130xc2x0 C.
The phosphorus pentahalide employed is PCl5 or PBr5, in particular PCl5.
The inert solvent employed is an aliphatic, cycloaliphatic or aromatic hydrocarbon or a mono- or polychlorinated aliphatic, cycloaliphatic or aromatic hydrocarbon.
Very suitable inert solvents are, for example, hexane, cyclohexane, methylcyclohexane, toluene, ethylbenzene, mesitylene, o-xylene, m-xylene, p-xylene, technical mixtures of isomeric xylenes, methylene chloride, tetrachloroethane, chlorobenzene, dichlorobenzene or chlorotoluene. It is also possible to use mixtures of solvents.
The phosphorus pentahalide is suspended or dissolved in the inert solvent and the reaction is carried out with the addition of the aforementioned nitrogen-containing compounds.
This results in compounds of the formula (1) in which Xxe2x88x92 is a halide. If required, the halide can be exchanged for another one of the aforementioned anions by metathesis.
The invention further relates to the use of the compounds of the formula (1) as catalyst and cocatalyst for phase-transfer reactions, nucleophilic substitutions and halogen-fluorine exchange reactions.
The invention further relates to the use of the mixtures of substances comprising at least one compound of the formula (1) and at least one compound selected from the group of quaternary ammonium compounds of the formula (2), quaternary ammonium salts or phosphonium salts of the formula (3), polyethers of the formula (4) and crown ethers as catalyst for phase-transfer reactions, nucleophilic substitutions and halogen-fluorine exchange reactions.